KR102588237B1 - insulation device - Google Patents

Abstract

Embodiments of the present disclosure relate to thermal insulation devices and methods of forming such thermal insulation devices. In one example, a method of forming an insulating device includes connecting a barrier material to a mold; Injecting a polyurethane foam composition into a mold, wherein the polyurethane foam composition includes polyol, isocyanate, and supercritical carbon dioxide; curing the polyurethane foam composition to form polyurethane foam; and applying a vacuum to the mold to provide a pressure of 1 millibar to 500 millibars.

Description

insulation device

Embodiments relate to insulating devices, and more particularly, to insulating devices formed from a polyurethane foam composition comprising polyol, isocyanate, and supercritical carbon dioxide, and methods of forming the same.

Polyurethanes can be used in many applications. Depending on the application, polyurethanes with special properties may be desirable.

Polyurethane foam is used in many applications. For example, polyurethane foam can be used in the home appliance industry as well as the construction industry, among other industrial sectors. For some applications, polyurethane foam may be used to provide insulation, among other properties.

The present disclosure provides a method of forming an insulating device, the method comprising: providing a barrier material to a mold; injecting a polyurethane foam composition into the mold, the polyurethane foam composition comprising polyol, isocyanate and supercritical carbon dioxide; curing the polyurethane foam composition to form polyurethane foam; and applying a vacuum to the mold to provide a pressure of 1 millibar to 500 millibars.

The present disclosure provides an insulating device, the device comprising: a mold; a barrier material connected to the mold; and a polyurethane foam inside the mold, wherein the polyurethane foam is formed by injecting the polyurethane foam composition into the mold and curing the polyurethane foam composition, wherein the polyurethane foam composition is It contains polyol, isocyanate and supercritical carbon dioxide, and a vacuum is applied to the mold to provide a pressure of 1 millibar to 500 millibars.

The above summary of the disclosure is not intended to describe each disclosed implementation or every embodiment of the disclosure. The following description more particularly illustrates example implementations. At various places throughout the application, guidance is provided through lists of examples in which the examples may be used in various combinations. In each case, the enumerated list serves only as a representative group and should not be construed as an exclusive list.

Described herein are insulating devices and methods of forming the insulating devices. For example, a method of forming an insulating device may include providing a barrier material to a mold; injecting a polyurethane foam composition into the mold, the polyurethane foam composition comprising polyol, isocyanate and supercritical carbon dioxide; curing the polyurethane foam composition to form polyurethane foam; and applying a vacuum to the mold to provide a pressure of 1 millibar to 500 millibars. Advantageously, embodiments of the present disclosure may provide improved thermal conductivity and/or improved manufacturability compared to other insulating panels, among other advantages.

Some previous insulation panels utilizing polyurethane foam are manufactured at atmospheric pressure, i.e. the polyurethane foam is in fluid communication with the external environment of the insulation panel. In other words, fluids, for example air, can pass into and out of the insulating panels containing polyurethane foam. However, these previously insulated panels may have a thermal conductivity of about 18 milliwatts per meter - Kelvin [mW/(m·K)] or more, which may be undesirable and/or insufficient thermal conductivity for many applications.

Some other older insulated panels using polyurethane foam can be called vacuum insulated panels. Vacuum insulated panels are manufactured at high vacuum, such as pressures below 1 millibar (mbar), and the polyurethane foam typically has an average pore diameter of greater than 200 micrometers (μm). These vacuum insulated panels are sealed at these pressures to ensure that the polyurethane foam is not in fluid communication with the external environment of the vacuum insulated panels. In other words, fluids such as air cannot pass in or out of vacuum insulated panels containing polyurethane foam. The thermal conductivity of the vacuum insulation panel may be about 5 mW/(m·K) or less. However, due to the high vacuum associated with vacuum insulated panels, the manufacture of vacuum insulated panels may require specific equipment and/or special manufacturing conditions, which may result in increased costs for the vacuum insulated panels and/or time for processing the vacuum insulated panels. may be needed. Additionally, due to the high vacuum associated with vacuum insulated panels, the shape of the vacuum insulated panels may be limited. For example, it may be difficult or even infeasible to manufacture vacuum insulation panels of irregular shape, for example panels with sharp protrusions and/or angles within the panel. As such, compared to other insulating panels, embodiments of the present disclosure may provide improved manufacturability.

As mentioned, an insulating device and a method of forming the insulating device are described herein. Embodiments of the present disclosure provide thermal insulating devices with a thermal conductivity of 8 mW/(m·K) to 14 mW/(m·K), which may be desirable for many applications. All individual values and subranges from 8 mW/(m·K) to 14 mW/(m·K) may be included; For example, an adiabatic device may have a lower limit of 8 mW/(m·K), 8.5 mW/(m·K), 9 mW/(m·K) or 9.5 mW/(m·K) to 14 mW/(m ·K), 13.5 mW/(m·K), 13.25 mW/(m·K), or 13 mW/(m·K). This thermal conductivity can be achieved through the synergistic action of the insulating device components further considered herein.

Embodiments of the present disclosure provide thermal insulation devices comprising polyurethane foam. Polyurethane foam can be formed from polyurethane foam compositions. Polyurethanes are polymers containing chains of units joined by carbamate linkages, which may be referred to as urethane linkages. Polyurethanes can be formed by reacting isocyanates with polyols in the presence of a blowing agent. As used herein, “polyol” refers to a molecule having an average of more than 1.0 hydroxyl groups per molecule. A foam is a dispersion of a gas dispersed in a liquid, solid and/or gel material.

Embodiments of the present disclosure provide that polyurethane foam compositions can include polyols. A variety of polyols can be used. Examples of polyols include, but are not limited to, polyester-polyols, polyether-polyols, and combinations thereof.

Polyester-polyols include, for example, organic dicarboxylic acids having 2 to 12 carbon atoms, including aromatic dicarboxylic acids having 8 to 12 carbon atoms and polyhydric alcohols, including diols having 2 to 12 carbon atoms. It can be prepared from carboxylic acid. Examples of suitable dicarboxylic acids include succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid and isomeric naphthalene. -There is dicarboxylic acid. Dicarboxylic acids can be used individually or mixed with each other. The free dicarboxylic acids may be replaced by corresponding dicarboxylic acid derivatives, for example dicarboxylic acid esters of alcohols having 1 to 4 carbon atoms or dicarboxylic acid anhydrides. Some specific examples include, for example, a dicarboxylic acid mixture comprising succinic acid, glutaric acid and adipic acid in a ratio of 20 to 35 : 35 to 50 : 20 to 32 parts by weight, and adipic acid, and phthalic acid and/ or mixtures of phthalic anhydride and adipic acid, phthalic acid or mixtures of phthalic anhydride, isophthalic acid and adipic acid, or dicarboxylic acid mixtures of succinic acid, glutaric acid and adipic acid and mixtures of terephthalic acid and adipic acid or succinic acid. , dicarboxylic acid mixtures of glutaric acid and adipic acid can be used. Examples of dihydric and polyhydric alcohols include, inter alia, ethanediol, diethylene glycol, 1,2- and 1,3-propanediol, dipropylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6- These include hexanediol, 1,10-decanediol, glycerol, and trimethylolpropane. Some specific examples include ethanediol, diethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol or mixtures of at least two of these diols, especially 1,4-butanediol, 1,5- A mixture of pentanediol and 1,6-hexanediol is provided. Moreover, polyester-polyols prepared from lactones such as ε-caprolactone or hydroxycarboxylic acids such as ω-hydroxycaproic acid and hydrobenzoic acid can also be used.

Some embodiments of the present disclosure provide that the polyester-polyol, without or in the presence of an esterification catalyst, in an inert gas atmosphere, such as nitrogen, carbon monoxide, helium, argon, from about 150° C. to about Organic, for example aliphatic, preferably aromatic polycarboxylic acids and mixtures of aromatic and aliphatic polycarboxylic acids, and/ or a derivative thereof, and polycondensation of a polyhydric alcohol, and the desired acid value may be less than 10, and in some cases preferably less than 2. Some embodiments of the present disclosure provide that the esterification mixture is polycondensed at the above-mentioned temperature under ambient pressure, and subsequently less than 500 millibars, e.g. For example, polycondensation is carried out under a pressure of 50 to 150 mbar. Examples of suitable esterification catalysts include, but are not limited to, iron, cadmium, cobalt, lead, zinc, antimony, magnesium, titanium and tin catalysts in the form of metals, metal oxides or metal salts. Polycondensation can also be carried out in the liquid phase in the presence of diluents and/or entrainers such as benzene, toluene, xylene or chlorobenzene for removal of condensate by, for example, azeotropic distillation.

Polyester-polyols can be prepared by polycondensing organic polycarboxylic acids and/or their derivatives with polyhydric alcohols at a molar ratio of 1:1 to 1:1.8, for example, 1:1.05 to 1:1.2.

Additionally, anionic polymerization can be used. For example, as a catalyst, an alkali metal hydroxide, such as sodium hydroxide or potassium hydroxide, or an alkali metal alkoxide, such as sodium methoxide, sodium ethoxide, potassium ethoxide or potassium isopropoxide, may be used as a catalyst. Lewis acids, inter alia such as antimony pentachloride, from one or more alkylene oxides having 2 to 4 carbon atoms in the alkylene moiety, with the addition of at least one initiator molecule containing 2 to 8 reactive hydrogen atoms in the form. Boron fluoride etherate, or by cationic polymerization using bleaching earth as a catalyst.

Examples of suitable alkylene oxides include tetrahydrofuran, 1,3-propylene oxide, 1,2- and 2,3-butylene oxide, styrene oxide, preferably ethylene oxide and 1,2-propylene oxide. It is not limited to this. The alkylene oxides may be used individually, alternatively one by one, or as a mixture. Examples of suitable initiator molecules include water, organic dicarboxylic acids such as succinic acid, adipic acid, phthalic acid and terephthalic acid, and various amines such as, but not limited to, aliphatic and aromatic having 1 to 4 carbon atoms in the alkyl moiety. , unsubstituted or N-mono-, N,N- and N,N'-dialkyl-substituted diamines such as unsubstituted or mono- or dialkyl-substituted ethylenediamine, diethylenetriamine, triethylene Tetramine, 1,3-propylene-diamine, 1,3- and 1,4-butylene diamine, 1,2-, 1,3-, 1,4-, 1,5- and 1,6-hexamethylene Diamines, aniline, cyclohexanediamine, phenylenediamine, 2,3-, 2,4-, 3,4- and 2,6-tolylenediamine and 4,4'-, 2,4'- and 2,2 '-diaminodiphenylmethane, but is not limited thereto. Other suitable initiator molecules include alkanolamines such as ethanolamine, N-methyl- and N-ethylethanolamine, dialkanolamines such as diethanolamine, N-methyl- and N-ethyldiethanolamine. , and trialkanolamines, such as triethanolamine and ammonia, and polyhydric alcohols, especially dihydric and/or trihydric alcohols, such as ethanediol, 1,2- and 1,3-propanediol, diethylene glycol, dipropylene glycol. , 1,4-butanediol, 1,6-hexanediol, glycerol, trimethylolpropane, pentaerythritol, sorbitol and sucrose, polyhydric phenols such as 4,4'-dihydroxydiphenylmethane and 4,4' -dihydroxy-2,2-diphenyl propane, resols, for example oligomeric products of the condensation of phenol with formaldehyde, and Mannich condensates of phenol, formaldehyde and dialkanolamines, and melamine.

One or more embodiments of the present disclosure provide that the polyol comprises at least one alkylene oxide, such as ethylene oxide or 1,2-propylene oxide or 1,2-propylene oxide and ethylene oxide, with at least two reactive hydrogen atoms. and a polyether-polyol prepared by anionic polyaddition as an initiator molecule on at least one aromatic compound containing at least one hydroxyl, amino and/or carboxyl group. Examples of initiator molecules include aromatic polycarboxylic acids, such as hemimellitic acid, trimellitic acid, trimesic acid, preferably phthalic acid, isophthalic acid and terephthalic acid, or mixtures of at least two polycarboxylic acids, hydroxyl carboxylic acids such as salicylic acid, p- and m-hydroxybenzoic acid and gallic acid, aminocarboxylic acids such as anthranilic acid, m- and p-aminobenzoic acids, polyphenols such as resorcinol, According to one or more embodiments of the present disclosure, dihydroxydiphenylmethane and dihydroxy-2,2-diphenylpropane, Mannich condensate of phenol, formaldehyde and dialkanolamine, preferably diethanolamine. , and aromatic polyamines such as 1,2-, 1,3- and 1,4-phenylenediamines such as 2,3-, 2,4-, 3,4- and 2,6-thol. rylenediamine, 4,4'-, 2,4'- and 2,2'-diamino-diphenylmethane, polyphenyl-polymethylene-polyamine, e.g. dia as formed by condensation of aniline with formaldehyde There are mixtures of mino-diphenylmethane and polyphenyl-polymethylene-polyamine, and mixtures of at least two polyamines.

Examples of hydroxyl-containing polyacetals include compounds that can be prepared from diethylene glycol, triethylene glycol, 4,4'-dihydroxyethoxydiphenyldimethylmethane, hexanediol, and formaldehyde. Suitable polyacetals can also be prepared by polymerizing cyclic acetals.

Examples of hydroxyl-containing polycarbonates include, for example, 1,3-propanediol, 1,4-butanediol and/or 1,6-hexanediol, diethylene glycol, triethylene glycol or tetraethylene glycol. It can be prepared by reacting the diol with a diaryl carbonate, such as diphenyl carbonate or phosgene.

As contemplated herein, polyols may be referred to as formulated polyols. The formulated polyol may be a mixture, e.g., a blend, of multiple polyols and/or additives contemplated herein. For example, the formulated polyol may include a number of blowing agents, catalysts, fillers, flame retardants, chain extenders or crosslinking agents, colorants, and/or combinations thereof.

Examples of commercially available polyols include, but are not limited to, polyols sold under the trade names VORANOL™, TERCAROL ^™ , and VORATEC™, among others. Embodiments of the present disclosure provide that polyurethane foam compositions can include isocyanates. A variety of isocyanates can be used, such as polyisocyanates. As used herein, “polyisocyanate” refers to a molecule having an average of more than 1.0 isocyanate groups per molecule, e.g., more than 1.0 functional groups on average. Many embodiments of the present disclosure provide that isocyanates can have three or more functionalities.

The polyisocyanate may include aliphatic polyisocyanate, cycloaliphatic polyisocyanate, araliphatic polyisocyanate, aromatic polyisocyanate, or a combination thereof. Examples of polyisocyanates include, but are not limited to, alkylene diisocyanates such as 1,12-dodecane diisocyanate; 2-ethyltetramethylene 1,4-diisocyanate; 2-methyl-pentamethylene 1,5-diisocyanate; 2-ethyl-2-butylpentamethylene 1,5-diisocyanate; tetramethylene 1,4-diisocyanate; and hexamethylene 1,6-diisocyanate. Examples of polyisocyanates include, but are not limited to, cycloaliphatic diisocyanates such as cyclohexane 1,3- and 1,4-diisocyanates and mixtures of these isomers; 1-isocyanato-3,3,5-trimethyl-5-isocyanato-methylcyclohexane; 2,4- and 2,6-hexahydrotolylene diisocyanate; and the corresponding isomeric mixtures, 4,4-, 2,2'- and 2,4'-dicyclohexylmethane diisocyanate; and corresponding isomer mixtures. Examples of polyisocyanates include, but are not limited to, araliphatic diisocyanates such as 1,4-xylylene diisocyanate and xylylene diisocyanate isomer mixtures. Examples of polyisocyanates include, but are not limited to, aromatic polyisocyanates such as 2,4- and 2,6-tolylene diisocyanates and the corresponding isomer mixtures, 4,4'-, 2,4'- and 2,2 '-Diphenylmethane diisocyanate and mixtures of the corresponding isomers, 4,4'- and 2,4'-diphenylmethane diisocyanate, mixtures of polyphenyl-polymethylene polyisocyanate, 4,4'-, 2,4' - and mixtures of 2,2'- diphenylmethane diisocyanate and polyphenyl-polymethylene polyisocyanate (crude MDI), and mixtures of crude MDI and tolylene diisocyanate. Polyisocyanates can be used individually or in combinations thereof.

One or more embodiments of the present disclosure provide that modified polyisocyanates can be used. Examples of modified polyisocyanates include, but are not limited to, ester-, urea-, biuret-, allophanate-, uretonimine-, carbodiimide-, isocyanurate-, urethedione- and/or urethane- Contains polyisocyanate. Examples include 4,4'-diphenylmethane diisocyanate, mixtures of 4,4'- and 2,4'-diphenyl methane diisocyanates, or crude MDI or 2,4- or 2,6-tolylene diisocyanate. , which are in each case modified by low molecular weight diols, triols, dialkylene glycols, trialkylene glycols or polyoxyalkylene glycols having a molecular weight of about 6,000 or less. Specific examples of di- and polyoxyalkylene glycols that can be used individually or in mixtures include diethylene, dipropylene, polyoxyethylene, polyoxypropylene and polyoxy-propylene-polyoxyethylene glycol, triol and/ Or there are tetrols. NCO-containing prepolymers containing 3.5 to 25% by weight, for example 14 to 21% by weight, based on total weight, of NCO and prepared from the polyester- and/or preferably polyether-polyols described herein, and 4,4'-diphenylmethane diisocyanate, mixtures of 2,4'- and 4,4'-diphenylmethane diisocyanate, 2,4- and/or 2,6-tolylene diisocyanate or crude MDI. This is also suitable. Furthermore, liquid polyisocyanates containing carbodiimide groups and/or isocyanurate rings and containing 15 to 33.6% by weight, for example 21 to 31% by weight, of NCO, based on the total weight, for example 4, 4'-, 2,4'- and/or 2,2'-diphenylmethane diisocyanate and/or 2,4' and/or 2,6-tolylene diisocyanate may also be used. Modified polyisocyanates can be mixed with each other or unmodified organic polyisocyanates, such as 2,4'- or 4,4'-diphenyl methane diisocyanate, crude MDI and/or 2,4- and/or Can be mixed with 2,6-tolylene diisocyanate. Many embodiments of the present disclosure provide that the isocyanates include, among others, polymerizable isocyanates such as polymethylenepolyphenylene isocyanate (PMDI).

Polyisocyanates can be prepared, for example, by known methods. For example, isocyanates can be prepared by phosgenation of the corresponding polyamines with the formation of polycarbamoyl chloride and its thermal decomposition to give polyisocyanates and hydrogen chlorides, or by, for example, reacting the corresponding polyamines with ureas and alcohols to give polyisocyanates. It can be prepared by a phosgene-free process, which obtains the carbamate and its thermal decomposition to obtain, for example, polyisocyanates and alcohols.

Polyisocyanates are commercially available. Examples of commercial polyisocyanates include, but are not limited to, the polyisocyanates sold under the trade names PAPI ^™ and VORATEC ^™ , such as VORATEC ^™ SD100, polymeric methylene diphenyl diisocyanate (MDI) available from The Dow Chemical Company. .

Embodiments of the present disclosure provide that polyurethane foam compositions can have an isocyanate index of 70 to 500. All individual values and subranges from 70 to 500 are included; For example, the polyurethane foam composition can have an isocyanate index from a lower limit of 70, 80, 90 or 100 to an upper limit of 500, 250, 150 or 130.

Embodiments of the present disclosure provide that the polyurethane foam composition includes supercritical carbon dioxide. Supercritical carbon dioxide, which may be referred to as a blowing agent, may be used to aid foam formation in polyurethane foam compositions. Advantageously, the use of supercritical carbon dioxide can help provide polyurethane foams with a number of desirable properties, as discussed further herein, which can help provide the thermal conductivity contemplated herein.

The supercritical carbon dioxide may be derived from 2 to 25 parts by weight of the polyurethane foam composition, based on 100 parts by weight of polyol used. All individual values and subranges from 2 to 25 parts by weight are included; For example, the supercritical carbon dioxide can range from a lower limit of 2, 5 or 8 parts by weight to an upper limit of 25, 23 or 20 parts by weight, based on 100 parts by weight of polyol used.

One or more embodiments of the present disclosure provide that the polyurethane foam composition can include a surfactant. As used herein, surfactants can also be used as cell openers. Examples of surfactants include silicone-based compounds such as silicone oils and organosilicon-polyether copolymers such as polydimethyl siloxane and polydimethylsiloxane-polyoxyalkylene block copolymers such as polyether modified polydimethyl. siloxanes and combinations thereof. Examples of surfactants include, inter alia, silica particles and silica airgel powders, as well as organic surfactants such as nonylphenol ethoxylate, and VORASURF™ 504, an ethylene oxide/butylene oxide block copolymer with relatively high molecular weight, and There are combinations of these. Surfactants are commercially available and include, among others, those available under trade names such as DABCO™, NIAX™, and TEGOSTAB™. Commercially available surfactants include surfactants available from Dearmate and Momentive, among other suppliers. One or more embodiments of the present disclosure provide that, when a surfactant is used, such surfactant is present in 0.1% to 10% of the total weight of the polyol used. All individual values and subranges from 0.1% to 10% are included; For example, the surfactant can range from a lower limit of 0.1, 0.2 or 0.3% to an upper limit of 10, 8.5 or 6.0%, based on the total weight of polyol used.

One or more embodiments of the present disclosure provide that polyurethane foam compositions can include catalysts, such as blowing catalysts, gel catalysts, trimerized catalysts, or combinations thereof, among others. As used herein, blowing catalysts and gel catalysts can be distinguished by their tendency to favor the urea (blow) reaction for blowing catalysts, or the urethane (gel) reaction for gel catalysts. Trimerization catalysts can be used to promote the reactivity of polyurethane foam compositions.

Examples of blowing catalysts, e.g., catalysts that may tend to favor a blowing reaction, include, but are not limited to, short chain tertiary amines, or tertiary amines containing oxygen. For example, the foaming catalyst includes, among others, bis-(2-dimethylaminoethyl)ether; Includes pentamethyldiethylene-triamine, triethylamine, tributyl amine, N,N-dimethylaminopropylamine, dimethylethanolamine, N,N,N',N'-tetra-methylethylenediamine and combinations thereof. do.

Gel catalysts, e.g., catalysts that may tend to favor a gel reaction, include, but are not limited to, organometallic compounds, cyclic tertiary amines containing several nitrogen atoms and/or long chain amines, and combinations thereof. It doesn't work. Organometallic compounds include organotin compounds, such as tin(II) salts of organic carboxylic acids, such as tin(II) diacetate, tin(II) dioctanoate, tin(II) diethylhexanoate. and tin(II) dilaurate, and dialkyltin(II) salts of organic carboxylic acids, such as dibutyltin diacetate, dibutyltin dilaurate, dibutyltin maleate and dioctyltin diacetate. There is. Bismuth salts of organic carboxylic acids, such as bismuth octanoate, can also be used as gel catalysts. Cyclic tertiary amines and/or long chain amines include dimethylbenzylamine, N,N,N',N'-tetramethylbutanediamine, dimethylcyclohexylamine, triethylenediamine, and combinations thereof.

Examples of trimerization catalysts include tris(dialkylaminoalkyl)-s-hexahydrotriazine, such as 1,3,5-tris(N,N-dimethylaminopropyl)-s-hexahydrotriazine; [2,4,6-tris(dimethylaminomethyl)phenol]; Potassium acetate, potassium octoate; tetraalkylammonium hydroxides, such as tetramethylammonium hydroxide; Alkali metal hydroxides such as sodium hydroxide; Alkali metal alkoxides such as sodium methoxide and potassium isopropoxide, and alkali metal salts of long chain fatty acids having 10 to 20 carbon atoms and combinations thereof. Some commercially available trimerization catalysts include, among others, DABCO® TMR-30, DABCO® K 2097; These include DABCO® K15, POLYCAT® 5, POLYCAT® 8, POLYCAT® 41, POLYCAT® 43, POLYCAT® 46, DABCO® TMR, and CURITHANE 52.

The catalyst may be used at 0.5% to 5.0% of the total weight of polyol used. All individual values and subranges from 0.5% to 5.0% are included; For example, the catalyst may range from a lower limit of 0.5, 0.6 or 0.7% to an upper limit of 5.0, 4.0 or 3.0% of the total weight of polyol used.

One or more embodiments of the present disclosure provide that the polyurethane foam composition may include one or more additional ingredients. Various additional components and/or different amounts of additional components may be used for various applications. Examples of additional ingredients include, among others, pigments, colorants, flame retardants, cross-linkers, chain extenders, antioxidants, bioretardant agents, and combinations thereof. One or more embodiments of the present disclosure provide that the polyurethane foam composition can include an opacifying agent. One example of an opacifying agent is carbon black.

As mentioned, the polyurethane foam composition can be injected into a mold, for example into a cavity. Implementations of the present disclosure provide that molds can have various shapes and/or sizes. One or more embodiments of the present disclosure provide that the mold is suitable for refrigeration applications, such as for thermal insulation. Advantageously, the mold may be of irregular shape and/or, in contrast to vacuum insulated panels, may have a number of sharp protrusions and/or angles within the mold.

Embodiments of the present disclosure include barrier materials. The barrier material can help reduce fluid flow into and out of the mold, for example, after the polyurethane foam has cured within the mold. The barrier material can be sealed to help maintain the desired pressure within the mold, as discussed further herein. The barrier material may have an oxygen permeability of between 1e-20 m ³ m/(m ² Pa day) and 1e-12_m ³ m/(m ² Pa day). 1e-20 m ³ m/(m ² Pa day) All individual values and subranges from to 1e-12_m ³ m/(m ² Pa day) are included; For example, barrier materials range from the upper limit of 1e-12, 1e-13, or 1e-14 m ³ m/(m ² Pa day) to 1e-20, 1e-19 or 1e-18 m ³ m/(m ² It can have an upper limit oxygen permeability of Pa day).

Additionally, the barrier material may have a water vapor permeability of 1e-15 m ³ m/(m ² Pa day) to 1e-10_m ³ m/(m ² Pa day). All individual values and subranges from 1e-15 m ³ m/(m ² Pa day) to 1e-10_m ³ m/(m ² Pa day) are included; For example, the barrier material may have a water vapor permeability ranging from a lower limit of 1e-15, or 1e-15m ³ m/(m ² Pa day) to an upper limit of 1e-10 or 1e-11m ³ m/(m ² Pa day). You can. Examples of barrier materials include, inter alia, those available under the trade name SARANEX ^™ .

The barrier material may be connected to the mold, for example, the barrier material may be secured to the mold through chemical adhesion, mechanical adhesion, support material, and combinations thereof. The barrier material may be located inside the mold and/or outside the mold. One or more embodiments of the present disclosure provide that a barrier material can be injected into a mold. For example, a fluid can be injected into a mold, and this fluid hardens within the mold to form a barrier material.

Multiple components of the polyurethane foam composition can be combined, such as mixed, before being injected into the mold. Many of the components of the polyurethane foam composition may not be combined with other components of the polyurethane foam composition before being injected into the mold. In other words, all components of the polyurethane foam composition do not need to be combined together before being poured into the mold.

One or more embodiments of the present disclosure provide that multiple components of the polyurethane composition, such as polyol, supercritical carbon dioxide, and/or surfactants, among others, can be combined prior to injection into the mold. This combination may be referred to as the “B” side, which in Europe may be referred to as the “A” side. Because carbon dioxide is in a supercritical state, any number of components can be combined in a vessel suitable to maintain a temperature and pressure at which carbon dioxide can be maintained in a supercritical state.

One or more embodiments of the present disclosure provide that multiple components of the polyurethane foam composition, such as polyisocyanates, may be included in the “A” side, which in Europe may be referred to as the “B” side. . The A and B sides can be combined to provide the isocyanate index contemplated herein.

One or more embodiments of the present disclosure provide that side A and side B can be combined, for example with an injection head, and then injected, almost simultaneously, into the mold to be filled. One or more embodiments of the present disclosure provide that reaction injection molding can be used.

As the components of the polyurethane foam composition are injected into the mold, foaming and polymerization occur to form polyurethane foam. Foaming and/or polymerization may continue until the mold is filled with polyurethane foam.

As mentioned, porosity from has a number of desirable properties that can help provide the thermal conductivity contemplated herein. For example, in contrast to other blowing agents, the use of supercritical carbon dioxide can help polyurethane foams have an average pore diameter of 1 micron to 100 microns. All individual values and subranges from 1 micron to 100 microns are included; For example, polyurethane foam can have an average pore diameter from a lower limit of 1 micron, 2 micron, 2.5 micron, 3 micron or 3.5 micron to an upper limit of 100 micron, 75 micron, 50 micron, 35 micron or 25 micron. One or more embodiments of the present disclosure provide that the average pore diameter has a coefficient of variation of less than or equal to 25%. For example, the average pore diameter may have a coefficient of variation of less than 25%, less than 20%, less than 15%, or less than 10%.

Embodiments of the present disclosure provide that the polyurethane foam can be an open cell foam. Open cell can be referred to as mutual communication. The polyurethane foam may have an open cell percentage greater than 90%, for example between 90% and 100%. For example, polyurethane foam can have an open cell percentage from a lower limit of 90%, 95%, 96% or 97% to an upper limit of 100%, 99.85%, 99.75% or 99.5%.

Embodiments of the present disclosure provide that polyurethane foam can have a porosity of 80% to 98%. All individual values and subranges from 80% to 98% are included; For example, polyurethane foam can have a porosity ranging from a lower limit of 80%, 82.5% or 85% to an upper limit of 98%, 97% or 95%.

Embodiments of the present disclosure provide that a vacuum can be applied to the mold to provide a pressure between 1 millibar and 500 millibars. All individual values and subranges from 1 millibar to 500 millibars are included; For example, a vacuum can be applied to the mold to provide a pressure ranging from a lower limit of 1 millibar, 5 millibars, 10 millibars, or 50 millibars to an upper limit of 500 millibars, 450 millibars, 400 millibars, or 350 millibars. To provide the desired pressure within the mold, a vacuum may be applied after curing the polyurethane foam composition within the mold.

Insulating devices as disclosed herein can be formed by applying a vacuum to a mold with polyurethane foam inside and then sealing the barrier material. The pressure within the mold is achieved by the application of a vacuum and can be maintained, for example, by a sealed barrier material during the operating life of the insulating device. The insulating device disclosed herein can be used in a variety of applications, for example in refrigerators, freezers and hot water storage tanks, among others, as well as in building applications, for example in insulation walls of household appliances.

The application of vacuum can provide that the fluid in the sealed mold, ie the fluid in the insulating device, such as carbon dioxide, can have a Knudsen number of 0.85 to 1.15. All individual values and subranges from 0.85 to 1.15 are included; For example, the fluid within the sealing mold can have a Knudsen number from a lower limit of 0.85, 0.90 or 0.95 to an upper limit of 1.15, 1.00 or 1.05.

As mentioned, pressure achieved by insulating device components, such as polyurethane foam and vacuum application, can advantageously provide a synergistic effect to achieve the thermal conductivity contemplated herein.

Example

In the examples, various terms and designations for substances are used, including, for example, the substances included in Table 1. In Table 1, F indicates functionality and OH n° indicates hydroxyl number.

[Table 1]

Example 1, a method of forming an insulating device, was performed as follows. Polyol A [SD301 (47.55 grams), CP260 (38 grams), T5903 (9.5 grams)], catalyst [PC-41 (0.57 grams), PC-5 (0.48 grams), PC-8 (1.9 grams)] and interface Activator L 6164 (2 grams) was added to a pressure reactor (100 ml Parr reactor) maintained at 10 MPa and 40°C. Supercritical carbon dioxide was injected into the pressure reactor to the extent of saturating the contents of the pressure reactor. To promote carbon dioxide saturation while stirring the contents of the pressure reactor, the temperature and pressure inside the pressure reactor were maintained for 30 minutes. Using a high pressure homogenizer, an emulsion was formed with the contents of the pressure reactor; The emulsion had droplets with a diameter ranging from about 5 nanometers to about 300 nanometers. When PAPI ^TM -135C isocyanate (101 g) was added to the pressure reactor and the contents of the pressure reactor were stirred for about 1 minute, a polyurethane foam composition was formed. After about 8 minutes, a polyurethane foam composition with a viscosity of about 0.5 Pa-s was injected into a mold (20 cm × 20 cm × 2.5 cm) lined on the inside with a barrier material (SARANEX ^™ NEX 23P). . The polyurethane foam composition was cured to form a polyurethane foam that completely filled the mold cavity; Vacuum was applied to achieve a mold cavity pressure of 10 millibars and seal the barrier material to provide the insulating device of Example 2.

The polyurethane foam of Comparative Example 2 was formed using the components listed in Table 2.

[Table 2]

The formulated polyol with the composition given above is added to the vessel and mixed with an impeller at 3000 rpm for about 1 minute; Afterwards, the contents of the vessel were allowed to equilibrate for approximately 1 hour. Isocyanate having the composition shown above was added to the container, and the contents were mixed with an impeller at 3000 rpm for about 10 seconds. The contents of the container were poured into a mold (30 cm × 20 cm × 5 cm) and cured to form Comparative Example A. Comparative Example A was cut (20 cm It was decided. For Example 2 and Comparative Example A: the average pore diameter was determined by scanning electron microscopy equipped with Image Pro Plus software; Percent open cells were determined by Micromeritics Accupyc II 1340 according to ASTM D2856; Porosity was determined by ASTM D792-00, including weighing the polymer foam in water using a sinker; Thermal conductivity was measured according to ISO 12939-01 using heat flow meter equipment HC-074 from EKO Instrument Trading Co., Ltd. The results are shown in Table 3.

[Table 3]

The data in Table 3 shows that Example 2 has desirable thermal conductivity as discussed herein. Additionally, compared to other insulating panels, Example 2 may advantageously provide improved manufacturability.

Claims (12)

A method of forming a heat insulating device, comprising:
Connecting the barrier material to the mold;
injecting a polyurethane foam composition into the mold, the polyurethane foam composition comprising polyol, isocyanate, and supercritical carbon dioxide;
curing the polyurethane foam composition to form polyurethane foam; and
Applying a vacuum to the mold to provide a pressure between 1 millibar and 500 millibars. According to paragraph 1,
The method of claim 1, wherein the polyurethane foam has an average pore diameter of between 2 microns and 100 microns. ◈Claim 3 was abandoned upon payment of the setup registration fee.◈ According to paragraph 1,
The method of claim 1, wherein the polyurethane foam has a porosity of 80% to 98%. ◈Claim 4 was abandoned upon payment of the setup registration fee.◈ According to paragraph 1,
The method of claim 1, wherein the isocyanate comprises isocyanic acid polymethylenepolyphenylene ester. ◈Claim 5 was abandoned upon payment of the setup registration fee.◈ According to paragraph 1,
The method of claim 1, wherein the barrier material has an oxygen permeability of between 1e-20 m ³ m/(m ² Pa day) and 1e-12_m ³ m/(m ² Pa day). According to paragraph 1,
The method further comprising combining the polyol, isocyanate and supercritical carbon dioxide in a pressure vessel. ◈Claim 7 was abandoned upon payment of the setup registration fee.◈ According to clause 6,
The method of claim 1, wherein the pressure vessel has a pressure greater than 100 bar. An insulating device formed by the method according to claim 1. ◈Claim 9 was abandoned upon payment of the setup registration fee.◈ According to clause 8,
An insulating device, wherein the insulating device has a thermal conductivity of less than or equal to 16 mW/(m·K) at a pressure of less than or equal to 500 millibars. As an insulating device,
Mold;
a barrier material connected to the mold; and
Includes polyurethane foam inside the mold,
The polyurethane foam is formed by injecting a polyurethane foam composition into the mold and curing the polyurethane foam composition, wherein the polyurethane foam composition includes polyol, isocyanate, and supercritical carbon dioxide, 1 A vacuum is applied to the mold to provide a pressure of from millibars to 500 millibars. delete delete